Nitrogen → HCID 18667335, compound

HRID 2257411Notes

Reaction equation

HRID 2257411 reaction equation
C(OC(N[C@H](C(N[C@H](C(NC(C(C1OC2C=CC=CC=2N=1)=O)CC([O-])=O)=O)C)=O)C(C)C)=O)C1C=CC=CC=1.[CH2:40]([O:47][C:48]([NH:50][C@H:51]([C:55]([NH:57][C@H:58]([C:60]([NH:62][CH:63]([C:72]([C:74]1[O:75][C:76]2[CH:82]=[CH:81][CH:80]=[CH:79][C:77]=2[N:78]=1)=[O:73])[CH2:64][C:65]([O:67][C:68]([CH3:71])([CH3:70])[CH3:69])=[O:66])=[O:61])[CH3:59])=[O:56])[CH:52]([CH3:54])[CH3:53])=[O:49])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1.FC(F)(F)C(O)=O.N#N>CCOCC.C(Cl)Cl.CO.C(Cl)Cl>[CH2:40]([O:47][C:48]([NH:50][C@H:51]([C:55]([NH:57][C@H:58]([C:60]([NH:62][C@H:63]([CH:72]([C:74]1[O:75][C:76]2[CH:82]=[CH:81][CH:80]=[CH:79][C:77]=2[N:78]=1)[OH:73])[CH2:64][C:65]([O:67][C:68]([CH3:69])([CH3:71])[CH3:70])=[O:66])=[O:61])[CH3:59])=[O:56])[CH:52]([CH3:54])[CH3:53])=[O:49])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1

Participants

8

Reactant 4

HCID 947NitrogenHCID 6422Trifluoroacetic acidHCID 22875509HCID 22875509, compoundHCID 22875514HCID 22875514, compound

Product 1

HCID 18667335HCID 18667335, compoundYield 69%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

N-(N-Benzyloxycarbonyl-(S)-valinyl-(S)-alaninyl)-3-amino-4-(2-benzoxazolyl)-4-oxobutanoate (63; Q). A solution of the ester 62 (95.0 mg, 0.16 mmol) in a 1:1 mixture of methylene chloride and trifluoroacetic acid (10.0 ml) was stirred for 1 h under a dry atmosphere of N2. The solution was then reduced in vacuo, taken up in ether and reduced again. This process was repeated six times to afford the crude product as an off white solid. Flash chromatography (95:5 methylene chloride/methanol) gave 60.0 mg (69%) of the title compound as a white solid. The product existed as a mixture of three isomers in CD3OD, consisting of the ketone form (one isomer, c 44%), and its acycloxy ketal form (two isomers at C-4, c. 56%): m.p. 156°-159° C. [α]D26 -45.6° (c 0.13, methanol); IR (KBr) 3440, 2967, 1713, 1703, 1638, 1531, 1427; 1H NMR (CD3OD) δ 7.93-7.24 (9H, m), 5.59 (1H, brt), 5.16-5.00 (2H, m), 5.0-4.78 (1H, m), 4.50-4.22 (1H, m), 3.95-3.81 (1H, m), 3.11 (2H, d, J=6.5), 3.05-2.92 (1H, m), 2.70-2.39 (1H, m), 2.08-1.89 (1H, m), 1.19-0.78 (9H, m). Anal. Calcd. for C27H30N4O8. 0.5H2O: C, 59.22; H, 5.71; N, 10.23. Found: C, 59.48, H, 5.36, N, 10.17. M.S. (+FAB); 539 (M+ +1), 91. ##STR114## (a) R1 =OCH3, R2 =H (b) R1 =H, R2 =OCH3

Workup

  1. customto afford the crude product as an off white solid

Sources & evidence

ORD record
ord-347681ba6557453f96c12acea011253f
Source dataset
uspto-grants-1997_08
Patent number
US05656627

Reaction notes

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